Condensation product



Patented June 13, 1944 2,351,311 v CONDENSATION raonuc'r Kurt Alder and Hans-Ferdinand Itickert. Cologne. Germany; vested in the Alien Property Custodian No Drawing. Original application December 17,

1938, Serial No. 246,492. Divided and this application May 24, 1941, Serial No. 395,000. In Germany December 22, 1937 7 Claims. (Cl. 260-648) wherein the dashes indicate the points of addition.

It being understood that in the reaction component designated by symbol B the unsaturated hibitors such as hydroqulnone, pyrogallol and the like may be added to the reaction mixture, particularly in case of working with butadiene-LS,

isoprene and 2.3-dimethylbutadiene. As stated above, the reaction is performed at an elevated temperature, it being impossible to give definite lower and upper limits, since the optimum reac-'- tion conditions depend on the nature of the starting materials and on the tendency of the butadienes and the like to form dimeric products. In general, the dimerization process occurs more slowly than the addition of the 2 reaction components. On the other hand, some of the dimeric products may be split up into the monomeric products at a high temperature, Whereas the addition products formed by the interaction of the 2 reaction components are-stable at such temperatures. Thus, in case of cyclopentadiene the reaction is preferably performed at 180 C. as at this temperature the dimerics are split up so that the addition process is nearly quantitative.

linkage is activated by another double bond as employed in the diene-synthesissuch as butadiene-LB, isoprene, 2.3-dimethylbutadiene- T15 2,cyclopentadiene, cyclohexadiene and anthracenel 'I'he'reaction is performed by simply heating the mixture of the starting materials, preferably in a closed vessel: As a matter of fact care must be taken that the reaction is performed under such conditions as to prevent any substantial polymerization. To thisend, polymerization in-;--

Starting materials of the first I type are vinyl esters of organic acids, vinyl halo- 7, .Igenides, dihalogen and trihalogen ethylenes. u Compounds of the latter type are those common- Other dienes such as anthracene do not show any tendency to form dimerics at the usual reaction temperature.

This application is a divisional of our application Ser. No. 246,492, filed December 17, 1938, now Patent 2,336,208 granted December '7, 1943.

The following examples illustrate the present invention without; however, restricting it thereto, the parts being by weight unless otherwise Stat-ed: I 1

parts of freshly distilled monomeric cyclopentadiene and parts of vinyl acetate are heated in an autoclave for 14 hours to After distilling off at normal pressure the excess vinyl acetate, the reaction mixture is subjected to distillation in vacuo. At 1'1 mm. pressure the following three fractions are obtained:

Parts 11: 77-140" 10 III: 140-l50 48 prepared therefrom by the addition of phenylazide has the melting point 147-148. By hydrogenation of the alcohol in an acetic acid The hydrotriazole solution with platinum oxide the a-norborneol is obtained which is described in- Annalen der Chemie, vol. 512, 172 (1934) FractionIII represents the addition product of 2 mols of cyclopentadiene and 1 mol of vinyl acetate. The said compound corresponds to the following constitution:

HC L CH l CH! ll Ha I II: E HG /CH H-OCOCH:

CH CH By saponiflcation with methylalcoholic potassium hydroxide there is obtained therefrom the corresponding unsaturated alcohol of melting point 83, which yields with phenylazide a hydrotria'zole of melting point 194-195.

Example 2 When replacing in the preceding example the 150 parts of vinyl acetate by 100 parts of vinyl formiate and working under the same conditions. the formiates of the two alcohols are obtained in formlof colorless oils of boiling point 75-80" (at 20 mm. pressure) or 14o-143 (at 20 mm. pressure) respectively. 7

Example 3 When heating equal parts by Volume of butadiene-1.3 and vinyl acetate with the addition of polymerization inhibitors for 12 hours in an autoclave and distilling off the reaction mixture in I vacuo, there is obtained besides some unchanged vinyl acetateand dimeric butadiene the addition product, of the components, 1. e. the A -cyclohexane-ol-l-acetate in form of a colorless oil of boiling point 1'73-1'75 which corresponds to the Example 4 When replacing in Example 3 the butadiene by 2.3-dimethyl butadiene and working up in the usual manner there is obtained the 3.4-dimethyl- A -cyclohexene-ol-l-acetate in form of a colorless oil of an intensively ester-lik smell which on saponificati'on with methylalcoholic potassium hydroxide is converted into the corresponding alcohol (phenyl urethane of melting point 112 6.).

Example 5 Bythe addition of A -cyclohexadiene and' I vinyl acetate there is obtained, when working according to the preceding examples, the bicyclic acetate of the following constitution:

m on, on: no Ha HOCO--CH| n which is converted into the corresponding unsaturated alcohol (phenylurethane of melting 75 point 125-126) by saponiiication with methylalcoholic potassium hydroxide.

7 Example 6 10 parts of anthracene in 120 parts of xylene are heated in an autoclave for 18 hours to 220-230 with the addition of 20 parts of vinyl acetate. The reaction being complete. the solvent and the excess vinyl acetate are evaporated, whereby the residue partly crystallizes; on sucking off and rinsing with methanol the precipitate proves to be identical with unchanged anthracene (1 part). 7 After ashort time the methanol containing mother liquor forms a mass of crystals which represent the addition product of the components.

Gn dissolving from alcohol colorless crystals of melting point 101 C. are obtained which probably correspond to the following constitution:

0n saponiflcation the ester yields the corresponding alcohol of melting point 142.

' Example 7 parts of vinyl chloride and 80 parts of cyclopentadiene are heated in an autoclave for 15 hours to PTO-180. On distilling off the unchanged vinyl chloride the residue is fractionated in vacuo. At 11 mm. pressure the following two fractions are obtained:

Parts I: 46-47 '13 II: 128-1312.; 28

Fraction 1 representsthe chloride of the following constitution:

The hydrotriazol which is obtained therefrom by the addition of phenylazide melts at -1162 Fraction II represents the addition product of 2 mols cyclopentadiene and 1 mol of vinyl chloride of the following constitution:

0H CH\ no L 021 I on,

ll Hz 4: CH! .L no 11 H.Cl

H n with phenylazide a hydrotriazol of melting point 195 is obtained.

Example 8 By a 15 hours heating of 175 parts of 1.2-dichloroethylene with parts of cyclopentadiene in an autoclave and after distilling oil the reaction product in vacuo at 11 mm. pressure as described in Example '7, there are obtained the following two addition products of 1 or 2 mol of cyclopentadiene and 1.2-dichloroethylene:

119 ij omcl at 11 mm. pressure; the melting point 148'; and

of boiling point 74-76" hydrotriazol shows the E of boiling point 146-148 at 11 mm. pressure; the hydrotriazol shows the melting point 210.

Example 9 When adding trichloro-ethylene to cyclopentadiene while heating the components in an autoclave at 175-185 the addition product 2 mols of the latter and the trichloroethylene of the following constitution is obtained:

This compound represents a colorless oil which boils in vacuo at 11 mm. pressure at 158-160. With phenylazide it yields a hydrotriazole of melting point 225-226".

We claim: I

1. The process of producing diene-synthesis products which comprises reacting a hydrocarbon compound containing two conjugated C==C double linkages with a halogenated ethylene compound of the formula:

wherein X stands for halogen and R1 and R: each stand for a member of the group consisting of halogen and hydrogen, the reaction being performed by heating a mixture of said compounds under such conditions as to prevent any substantial polymerisation.

under such conditions as to prevent any substantial polymerisation.

4. The process of producing diene-synthesis products which comprises reacting a hydrocarbon compound containing two conjugated C=C double linkages with trichlorethylene of the 'formula C12C=CHCL the reaction being performed by heating a mixture of said compounds under such conditions as to prevent any substantial polymerisation.

5. The process as defined in claim 1 wherein polymerisation is prevented by the addition of a Y polymerisation inhibitor.

6. The process as defined in claim 1 wherein polymerisation is prevented by the addition-of a polymerisation inhibitor selected from the class consisting of hydroquinone and pyrogallol.

7. The 'process as definedin claim 1 wherein the hydrocarbon containing the conjugated double linkages is selected from the class consisting of butadiene-L3; isoprene, 2.3-dimethylbutadiene- 1.3, cyclopentadiene, cyclohexadiene and anthra- KURT ALDER. HAN S-FERDINAND RICKERT.

' cene. 

